Composition of matter comprising a polymer of a vinylidene monomer and a polyalkanolamine destaticizing agent



' to be wetted by moisture from the air.

COMPOSITION OF MATTER COMPRISING A POLY- MER OF A VINYLIDENE MONOMER AND A XQIiEYALKANOL A M I N E DESTATICIZING Myron A. Coler, Scarsdale,and Arnold S. Louis, River-dale, N.Y.

No Drawing. Application March 30, 1956 Serial No. 574,957

14 Claims. (Cl. 260-32.6)

This invention relates to improved synthetic resin molding compositions and methods of making same and, in particular, to such molding materials which avoid the highly undesirable effects of electrostatic charge build-up during the molding operation.

This application is a continuation-in-part of our copending application entitled Non-electrostatic Molding Composition, Serial Number 556,396, filed December 30, 1955, now abandoned.

It has been found that the process of molding certain synthetic resins causes the generation of high electrostatic charges. This evidences itself frequently by the formation of crows feet, fern-like and zig-zag patterns through the attraction of fine dust particles from the atmosphere. Such patterns are sometimes erroneously interpreted as being molding flaws.

The literature discloses many additives for rendering ynthetic resins destaticized. Many of such additives depend on the property of deliqueacence to cause the article The moisture renders the surfaces of the article sufiiciently conductive to prevent the further accumulation of electrostatic charges. Molding operations are normally carried out at temperatures substantially in excess of the boiling point of water and, therefore, as molded, the molded article is relatively moisture-free and thus subject to the accumulation of electrostatic charges at the time of molding.

Still other prior known additives which are inherently destaticizing agents tend to undesirably affect the physical properties of the plastic. For example, a lowering of the heat distortion point may occur. There may also be a change in color, gloss, hardness or water absorption characteristics, or blemishes may result from decomposition of additives or evaporation of low boiling fractions. The resulting product may also become toxic if the additive is in itself toxic.

Our invention, disclosed hereinafter, provides a plastic composition which avoids the disadvantages of acquiring electrostatic charges and, in particular, which is not susceptible to electrostatic charging during the molding op eration or upon release from the mold.

This invention does not depend on deliquescent action and, therefore, produces results substantially independent of humidity. This advantage of the invention is important in the elimination of the tendency for dust patterns to form on freshly molded plastic articles.

We have found that selected polyalkanolamines may be incorporated into synthetic resin molding compositions to provide antistatic properties.

A totally unexpected advantage of the above-named group of additives was discovered during molding tests of material prepared in accordance with this invention It was found that the additives disclosed, hereinafter improved fiow properties of the base plastic so as to permit shorter molding cycles as well as improved filling of thin mold sections; reduced breakage of thin-walled moldings and easier mold release were obtained.

2,931,783 Patented Apr. 5, 1950 An object of this invention is, therefore, to provide a method for eliminating the formation of electrostatic charges on molded plastic articles.

Another object is to provide a plastic molding composition having improved molding properties.

Still another object is to provide a plastic molding composition having preferred flow properties when injection molded.

A particular object is to provide a plastic material which is substantially non-susceptible to acquiring electrostatic charges. 7

A particular object of this invention is to provide a method for'eliminating the formation of electrostatic charges on molded plastic articles during and especially immediately after the molding operation.

Another object is to provide articles comprising polystyrene compositions which are free of the effects of electrostatic charges.

Still another object of this invention is to provide an improved plastic composition and methods of making same.

A still different object is to reduce the electrostatic charge on polystyrene objects made by injection moldings.

A further object of this invention is to provide a polystyrene composition of superior molding properties.

Further objects and advantages will become apparent and still others will be pointed out with particularity as the following detailed description proceeds.

We have found that dialkanolamines and trialkanolamines in which the hydroxyalkyl groups contain 2 to 8 carbon atoms and which contain no cyclic groups impart highly desirable antistatic properties to resinous polymer molding compositions in which they are incorporated. In other words, only those diand tri-alkanolamines in which all other substituent groups as well as the alkanol groups have the alkyl type of carbon'structure may be used.

It is within the scope of this invention to employ the acid salts and quaternary ammonium salts of the above compounds.

Specific polyethanolamines which are especially useful for the purposes of this invention are triisopropanolamine and N-butyl diethanplarnine.

It has been discovered in the course of experimentation with materials of the type described above that certain polyalkanolamines substituted with short chain alkanol groups tend to cause pufling or the formation of blowholes during extrusion or molding. The permissible chain length is dependent on the degree of substitution in a manner which cannot be simply stated except to say that longer chains are excluded as the degree of substitution is decreased. The situation is adequately covered if only those polyalkanolamines having a vapor pressure less than 760 mm. at 225 C. are used. If more volatile compounds are used, gassing during extrusion or molding becomes objectionable.

While additives having the above described tendency to gas are obviously undesirable in compositions which are to be handled at high temperatures, such materials can be used to make up a minor proportion of the total additive when used in combination with preferred additives.

By incorporating any of the above mentioned additives or mixtures thereof in polystyrene or other resinous polymers the destaticizing properties are attained without incurring any of the undesirable features enumerated above. The quantity of additive employed is between 3 and 12% by weight based on the total product and preferably between 5 and 10%. The upper limit is a matter of choice dictated by considerations of economy and is not critical.

enemas For example, 15% or more may be used and the desired destaticizing results obtained, although at higher concentrations there is danger of affecting physical prop erties adversely.w

Be it observed that it will often be advantageous .to prepare a master-batch of resin with incorporated additive, said master-batch containing as much as 50% additive which is far more additive than is recommended for use in molding operations, and being later cut back by extrusion or by being otherwise blended with untreated resin. Such a concentrate may well be sold, particularly in the, clear or natural color for blending with untreated resin of various colors of its own color.

By way of illustration, there are given hereinafter a number ofexamples wherein the additive, quantity of additive and the resinous polymer employed are varied. Since hundreds of combinations are possible it becomes impractical to show more than a few typical compositions withadditives so selected from the described group as to show operability of the group as a whole and therefore such examples shall not be regarded as limiting in any sense.

Where it is desired to prepare a master-batch or to market a concentrated blending material, the procedures of Examples 11 and 13 are preferred. In plants where mass polymerization is employed the procedures of Examples 12 and 13 will be especially useful.

In cases where plastic chip is to be treated or where the polymerization methods in use are not adapted to taking advantage of the processes mentioned above, the process of Example 7 is preferred for its simplicity and freedom from extra drying steps.

Where it is desired to incorporate pigment in the plastic as Well as to render it antistatic the processes of Examples 1 and 2 are preferred. This procedure is claimed in our copending application entitled Process forMaking Plastic Compositions, Serial No. 532,132, filed September 2, 1955.

In carrying out this last referred to process, the additive is dissolved in a solvent which is a non-solvent for the plastics employed. The solution and plastic in comminuted form are then mixed together. The solvent is then removed so as to deposit the additive over the plastic particles.

In accordance with a particular example of this last mentioned procedure, from 0.5 to 1.2 pound of the additive is dissolved in two pounds of isopropyl alcohol. Sufficient comminuted resinous polymer to make a total of ten pounds of additive plus polymer is mixed with the solution. The alcohol is then evaporated in an exhaust oven at 65 C. for 36 hours with occasional agitation, so as to leave the polymer granules uniformly coated with said additive.

The coated material is then fed through a Windsor type RC-65 twinscrew extruder equipped with a series of /s" square orifices. The die and barrel are maintained at a suitable temperature for the particular polymer, such as 400 F. for polystyrene. The extruded material may then be chopped up into molding granules.

The molding granules may then be injection molded, as for example on a Reed-Prentice 8-ounce injection molding press with a heater temperature of 550 F. for polystyrene. For other polymers conventional molding ternperatures prescribed by the polymer supplier may be employed.

As a test of the effectiveness of the additive the resulting articles may be promptly, sprayed with fine bentonite dust by means of a hand sprayer. The dust will collect in patterns on charged areas. Additional moldings may be set aside and observed periodically for "several weeks. Using a Keithley electrostatic voltmeter, the potential may bemeasured between the molding and ground immediately after withdrawal from the mold. I

,As a control means identical articles may be molded from the same polymer not using the additive.

Example 1 The foregoing procedure was carried out using the following composition:

The dust test showed the absence of charged areas. The electrostatic voltmeter reading was about one volt.

One control article was sprayed with the bentonite dust immediately after molding and a well defined fernlike pattern was immediately apparent. The same control article yielded a 20 volt reading on the electrostatic voltmeter upon removal from the mold. After long term storage another unmodified polystyrene molding showed definite dustpatterns whereas the modified polystyrene article showed but a few isolated gravity deposited grains.

The molding characteristics of the modified polystyrene were judged to be superior to those of the control or unmodified polystyrene by the molding machine operator on the basis of obviously improved ease of mold release and lower breakage of thin walled moldings.

Example 2 The procedure of Example 1 was repeated with the exception that 0.1 gram of phthalocyanine blue was suspended in the alcohol and put through a colloid mill together with the additive prior to in corporation into the polystyrene. The resulting molded product was a uniform attractive pale blue color.

When tested as in Example 1, the molding and destaticizing characteristics were found to be identical to the treated product of Example 1.

Example 3 Example 1 was repeated with the same additive in a concentration of' 3% by weight of the total product. The resulting molding exhibited poor non-electrostatic properties, as measured by the Keithley voltmeter. A small amount of dust was collected in patterns after storage for one week. There was an improvement shown over the performance of the unmodified control specimen.

Example 4 Example 1 was repeated using 1.0 pound of the same additive and 9.0 pounds of polystyrene. A slight improvement in destaticizing properties was noted.

Example 5 The procedure of Example 1 was repeated with 0.6 pound of N-butyl diethanolamine and an extruder barrel and die temperature of 375 F. utilizing 9.4 pounds of polymethylmethacrylate as the resinous polymer. The resultant molding had substantially the same hardness as an unmodified control molding and exhibited excellent non-static and molding properties. The Keithley voltmeter reading was 1 volt directly after the molding operation.

Example 6 Example 7 0.7 pound of diisobutanolamine and 9.3 pounds of polystyrene granules as used in Example 1 were thoroughly mixed ina sigma blade mixer. The mixture was then extruded, chopped and molded as in Example 1. The molded articles showed no discernible electrostatic charge as measured on the Keithley meter. The molded articles showed no tendency to collect dust in patterns during a 30 day storage test.

Example 8 Example 1 was repeated using as the additive 0.6 pound of triethanolammonium acetate and 9.4 pounds of the polystyrene. The results were comparable.

Example 9 The procedure of Example 4 was repeated with an extruder barrel and die temperature of 350 F. utilizing 9.4 pounds of /a polyethylene pellets as the resinous polymer and 0.6 pound of the triethanolamine as the additive. Molding was carried out at a temperature of 350 F. Immediately after molding, a Keithley voltmeter reading of about one volt was noted. The contrcil specimen showed a voltmeter reading of over twenty vo ts.

Example 10 60 grams of triisopropanolamine dissolved in 60 grams of water, were incorporated into 666 grams of polystyrene emulsion containing 30% polystyrene solids.

740 grams of granulated polystyrene were placed in a Baker-Perkins mixer. With the mixer in operation, the polystyrene emulsion additive mixture was slowly added. The resultant slurry was then dried at 65 C. for 48 hours at which time it was found to be water-free. The resultant mixture which contained 6% of the additive, when molded as in Example 1, yielded moldings which when tested as in Example 1, exhibited destaticized characteristics similar to the modified product of Example 1.

Example I] 80 grams of diisobutanolamine dissolved in 100 grams of water were added to 400 grams of a 30% solids polystyrene emulsion. This mixture was spray-dried and gave a free flowing polystyrene powder containing. one part of the additive to three parts of polystyrene. The resultant concentrate was tumbled with 800 grams of a granulated polystyrene. The resultant blend was injection molded under conventional polystyrene molding conditions and yielded destaticized moldings having properties comparable to those produced by the procedures of Example 1.

Example 12 0.6 gram of at, a azodiisobutyronitrile was dissolved in 240 grams of monomeric styrene along with 60 grams of triisopropanolamine. The solution was placed in a heated agitated reaction kettle into which nitrogen was bubbled. The styrene solution was heated at 70 C. for 1 /2 hours until an exothermic reaction took place. The reaction was continued for an additional 30 minutes with the temperature being gradually increased to 90 C. until considerable polymerization took place as evidenced by an increase in viscosity. The mixture was tran ferred to air-free containers which were then sealed. The containers were maintained at a temperature of 90 C. for 48 hours. The resultant polymer was extruded, chopped and injection molded under normal polystyrene molding conditions. Moldings were clean and when rubbed with a wool cloth they would not become electrostatically charged as does unmodified polystyrene when so rubbed.

grams of triisopropanolamine and the solution was placed in a heated agitated reaction kettle into which n1trogen Considerable polymerization took place as evidenced by an increase in viscosity. Themixture was transferred to air-free containers which were then sealed. The containers were held, at C. for 48' hours} The resultant polymer was extruded and chopped into granules. In the'succeeding step of the operation, 400 grams of the resulting granules were mixed with 600 grams of untreated polystyrene granules, extruded, chopped andinjection molded under normal polystyrene molding conditions. The resulting moldings were similar in quality to those made in Example 1.

For the purpose of illustrating the invention, examples have been shown of the application of our invention to plastic alloys of polystyrene, polyethylene, polyvinylchloride and polymethylmethacrylate and their copolymers. We wish it to be understood that the invention may be utilized in treating other polymers such as polyacrylonitrile, polyfluoroethylene, polytrifiuoromonochloroethylene, polybutadienes, halogenated polystyrenes, and mixtures and copolymers of these materials.

The term vinylidene as used herein is intended to define monomers containing a polymerizable unsaturated structure and is generic to vinyl and vinylidene monomers. Each of the polymers specifically exemplified in the preceding examples, namely: polystyrene, polymethylmethacrylate, polyvinyl chloride and polyethylene is a polymer of a vinylidene monomer, so defined.

By plastic alloy as used herein we intend to encompass compositions comprising two or more types of polymeric molecules whether prepared by copolymerization or by intimate mixing.

Mixtures of the various additives may be employed providing the total amount is within the disclosed proportions for a single specie.

While we have disclosed what is at present considered the best mode for carrying out our invention, we appreciate that it will be obvious to those skilled in the art that various changes and modifications may be made therein without departing from the invention, and it is, therefore, aimed in the appended claims to cover all such changes and modifications as fall within the true spirit and scope of the invention.

What we claim is:

1. A composition of matter comprising a polymer of a vinylidene monomer and containing a destaticizing agent consisting of an acyclic polyalkanol amine selected from the group consisting of: dialkanol amines and trialkanol amines wherein between 2 and 8 carbon atoms are present in each of the hydroxyalkyl groups attached to the nitrogen atom; the destaticizing agent comprising at least 5% and not over 10% by weight of the composition, based on the weight of the polymer.

2. The composition of claim 1 wherein said polyalkanolamine is triethanolamine.

3. The composition of claim 1 wherein said alkanolamine is triisopropanolamine.

4. The composition of claim 1 wherein said polyalkanolamine is diisobutanolamine.

5. The composition of claim 1 wherein said alkanolamine is triisopropanolamine hydrochloride.

6. The composition of claim 1 wherein said alkanolamine is N-butyl diethanolamine.

7. The composition of claim 1 wherein said polymer is polystyrene.

8. The composition of claim 1 wherein said polymer is polyvinylchloride.

'7 8 f9. The'ofiap'casit iojn of blaiifi "1vhrein'saii1polyrher is 13. The composition of claim 1 wherein the polymer ifilymjetliylniethacryla'te. v is polystyrene "and the Vpolyalkanolamine is triisopropanol IO The 'coiiipositi'on "of claim 1 wherein said resin is ainine. polyethylene. I 14. The composition of claim 12 wherein the polymer 1 1 composition of claim 1 wherein said polymer is 5 is polystyrene. a i'nixiture containing polymers of monomers selected from the group consisting of ncrylonitrile, styrene, and References Cited in the file of this Patent butadiene. UNITED STATES PATENTS 12. A destaticized composition of matter according to 1 932 339 G g O 31, 1933 claim 1 wherein the additive is one having a vapor pres- 10 2,237,183 M h 'et a1 June 23, 1942 'sureiess than 760 *mm. at 225 C. 2,529,315 Serniuk Nov. 7, 1950 

1. A COMPOSITION OF MATTER COMPRISING A POLYMER OF A VINYLIDENE MONOMER AND CONTAINING A DESTATICIZING AGENT CONSISTING OF AN ACYCLIC POLYALKANOL AMINE SELECTED FROM THE GROUP CONSISTING OF: DIALKANOL AMINES AND TRIALKANOL AMINES WHEREIN BETWEEN 2 AND 8 CARBON ATOMS ARE PRESENT IN EACH OF THE HYDROXYALKYL GROUPS ATTACHED TO THE NITROGEN ATOM, THE DESTATICIZING AGENT COMPRISING AT LEAST 5% AND NOT OVER 10% BY WEIGHT OF THE COMPOSITION, BASED ON THE WEIGHT OF THE POLYMER. 